WO2006129991A1 - Recepteur anionique et electrolyte utilisant ce recepteur - Google Patents

Recepteur anionique et electrolyte utilisant ce recepteur Download PDF

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WO2006129991A1
WO2006129991A1 PCT/KR2006/002161 KR2006002161W WO2006129991A1 WO 2006129991 A1 WO2006129991 A1 WO 2006129991A1 KR 2006002161 W KR2006002161 W KR 2006002161W WO 2006129991 A1 WO2006129991 A1 WO 2006129991A1
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tegmp
pegmpc
tegmpc
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tfsa
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Hee Jung Kim
Won Sil Lee
Ki-Beom Park
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Hee Jung Kim
Won Sil Lee
Ki-Beom Park
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a novel anion receptor, and a nonaqueous liquid electrolyte and a gel or solid polymer electrolyte containing the same. More specifically, the present invention relates to a novel anion receptor, which is a cyclic siloxane compound having an amine substituted with electron withdrawing groups or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups and which is added to enhance ionic conductivity and cation transference number of electrolytes, thereby increasing the electrochemical stability of alkali metal batteries using the electrolytes, and a nonaqueous liquid electrolyte and a gel or solid polymer electrolyte containing the anion receptors.
  • a novel anion receptor which is a cyclic siloxane compound having an amine substituted with electron withdrawing groups or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side
  • Anion receptors improve anion stability by the interaction between a Lewis acid and a Lewis base.
  • These anion receptors are compounds having electron deficient atoms (N and B), which facilitate the movement of lithium cations (Li + ) by coordinating electron- rich anions around to interfere with forming ion pairs between the anions and the lithium cations.
  • the first known anion receptors are aza-ether compounds containing cyclic or linear amides, by which N atoms in amides substituted by perfluoroalkylsulfonyl group become electron deficient and interact with electron-rich anions through coulombic attraction (J. Electrochem. Soc, 143 (1996) 3825, 146 (2000) 9).
  • aza-ethers have drawbacks that they exhibit limited solubility in polar solvents adopted to the typical nonaqueous electrolytes and electrochemical stability window of electrolytes containing LiCl salt does not meet the commercial need of battery voltage 4.0V required of anode materials.
  • aza-ethers are unstable to LiPF 6 (J. Electrochem. Solid-State Lett., 5 (2002) A248). That is, chemically and thermally unstable LiPF 6 is in equilibrium with solid LiF and PF 5 gas even at room temperature, and production of PF 5 gas makes the equilibrium moved towards generating PF 5 gas.
  • LiPF 6 (s) ⁇ ⁇ LiF (S) + PF 5 (g)
  • PF 5 has a tendency to initiate a series of reactions such as ring-opening polymerization or breaking an ether bond composed of atoms having a lone- pair electrons, e.g., oxygen or nitrogen. Meanwhile, PF 5 , a relatively strong Lewis acid, is known to attack electron pairs. Due to high electron density, aza-ethers are promptly attached by PF 5 (J. Power Sources, 104 (2002) 260). This is a major drawback to commercialize aza-ether compounds. To resolve this problem, McBreen et al. synthesized an anion receptor comprising boron as an electron deficient atom substituted by an electron withdrawing group using the same means (J. Electrochem.
  • solid polymer electrolytes are not only convenient to use because they do not cause liquid leakage and are superior in vibration-shock resistance, but also suitable for use in light, small portable electronics equipments, wireless information & communication equipments and home appliances, and high capacity lithium polymer secondary batteries for electric vehicles because they have very low self-discharge and can be used even at a high temperature. Therefore, many extensive researches have been done on improvement of these performances.
  • a PAO (polyalkylene oxide) type solid polymer electrolyte was first discovered by P. V. Wright (British Polymer Journal, 7, 319), and it was named as an "ionic conductive polymer" by M.
  • a solid polymer electrolyte is composed of lithium salt complexes and a polymer containing electron-donating atoms, such as, oxygen, nitrogen and phosphor.
  • a solid polymer electrolytes is polyethylene oxide (PEO) and lithium salt complexes thereof. Because these have ionic conductivity as low as 10 ⁇ 8 S/cm at room temperature, they cannot be applied to electrochemical devices that usually operate at room temperature. A reason why the PAO type solid polymer electrolytes have very low ionic conductivity at room temperature is because they are easily crystallized and thus, motion of molecular chains therein is restricted.
  • Li order to increase motility of molecular chains the crystalline area existing in the polymer structure should be minimized while the amorphous area therein should be expanded.
  • a research to achieve such has been and is under way by using a siloxane having a flexible molecular chain (Marcromol. Chem. Rapid Commun., 7 (1986) 115) or a phosphagen (J. Am. Chem. Soc, 106 (1984) 6845) as a main chain, or by introducing PAO having a relatively short molecular length as a side branch (Electrochem. Acta, 34 (1989) 635).
  • net-shaped solid polymer electrolytes are prepared by introducing at least one crosslmkable functional group to the PAO as a terminal group.
  • ionic conductivity of such electrolytes at room temperature is as low as 10 "5 ⁇ 10 "4 S/cm which is not suitable for use in lithium batteries operating at room temperature conditions, so continuous researches have been made to improve the ionic conductivity.
  • This problem was resolved by Abraham et al. who introduced polyethylene oxide with low molecular weight into a vinylidenhexafluoride - hexafluoropropene copolymer to enhance ionic couductivity (Chem. Mater., 9 (1997) 1978).
  • the CF 3 radical thusly produced takes a hydrogen atom from the PEO polymer chain and forms HCF 3 .
  • a C-O-C- functional group is formed and the main chain of the polymer therein is cut off.
  • CH 3 produced by chain scission together with the CF 3 radical attack the chain or break a C-O bond.
  • a Li-O-R compound thusly formed is attached to the electrode surface and the electrode surface is passivated.
  • an object of the present invention to provide a novel anion receptor, which is a cyclic siloxane compound having an amine substituted with electron withdrawing groups or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups and which enhances ionic conductivity and cation transference number of electrolytes containing it, thereby increasing the electrochemical stability of alkali metal batteries using the electrolytes.
  • R 1 and R 2 independently represents a hydrogen atom, or an electron withdrawing functional group selected from the group consisting Of -SO 2 CF 3 , -CN, -F, -Cl, -COCF 3 and -SO 2 CN, but do not both simultaneously represent a hydrogen atom;
  • R 3 represents a hydrogen atom or a cyano group
  • R 5 and R 6 independently represents a hydrogen atom or a methyl group
  • R 7 and the other R 7 in the formula each independently represents an alkyl, an alkenyl, an alkyl halide, an alkenyl halide, an alkanol, a halogen, a hydrogen atom or a hydroxyl group
  • Y and Z independently represent O, S, CO, OCO, OCOO or COO; n is an integer from 1 to 1000; o, p, and q are integers from O to 1000, respectively; and r and s are integers from 0 to 20, respectively, whose sum is at least 1.
  • the compound of the Formula 1 functions as an anion receptor in an electrolyte and preferred examples of the compound include C 4 -4TFSA; C 4 -4TFSI; C 4 -2TFSA-2TEGMP; C 4 -2TFSA-2PEGMP; Q-2TFSA-2TEGMPC; C 4 -2TFSA-2PEGMPC; C 4 -2TFSA-2CN; C 4 -2TFSA-2CPP; C 4 -2TFSA-TEGMP-CPP; C 4 -2TFSA-PEGMP-CPP; C 4 -2TFSA- TEGMPC-CPP; C 4 -2TFSA-PEGMPC-CPP; C 4 -2TFSA-CN-CPP; C 4 -2TFSA-TEGMP-CN; C 4 -2TFSA-PEGMP-CN; Q-2TFSA-TEGMPC-CN; C 4 -2TFSA-PEGMP-CN; C 4 -2TFSA- TEGMP-PEGMPC; C 4 -2TFS A-PEGMP-PEGMPC; C 4
  • TFSA-DFA-TFAC-PEGMPC C 4 -TFSA-DFA-TFAC-CN; C 4 -TFSA-DFA-TFAC-CPP;
  • TFSA-DCN-DCA-CPP C 4 -TFSA-DFA-DCA-TEGMP; C 4 -TFSA-DFA-DCA-PEGMP;
  • DCN-DCA-TFAC DCN-DCA-TFAC; C 4 -TFSA-DFA-DCA-TFAC; C 4 -TFSA-DCN-DFA-DCA or C 4 -DCN-
  • the nonaqueous liquid electrolyte and a gel or solid polymer electrolyte of the present invention comprises at least one of the novel anion receptors represented by the Formula 1 , which is composed of a cyclic siloxane compound having an amine substituted with electron withdrawing groups or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups.
  • the amine substituted with electron withdrawing groups increases the dissociation of alkali metal salts and therefore, enhances electronegativity and cation transference number.
  • nitrogen in the amine becomes electron deficient by electron withdrawing groups such as -SO 2 CF 3 , - CN, -F, -Cl, -COCF 3 and -SO 2 CN, and forms electrically neutral complexes with anions of alkali metal salts. In this manner, the dissociation of alkali metal salts into ions is promoted.
  • electron withdrawing groups such as -SO 2 CF 3 , - CN, -F, -Cl, -COCF 3 and -SO 2 CN
  • the anionic receptor represented by the Formula 1 can be synthesized by any known method.
  • the compound of the Formula 1 can be synthesized by hydrosilylating a compound represented by the following Formula 2 (the starting material) with allyl trifluoro sulfonamide, polyalkylene glycol allyl ether, allyl cyanide, and allyl propylene carbonate.
  • Formula 2 the starting material
  • allyl trifluoro sulfonamide polyalkylene glycol allyl ether
  • allyl cyanide allyl propylene carbonate
  • the present invention provides electrolytes containing the anion receptor represented by the compound of the Formula 1 , and the electrolytes comprise nonaqueous liquid electrolytes, gel polymer electrolytes and solid polymer electrolytes.
  • the nonaqueous liquid electrolyte of the present invention comprises (i) an anion receptor of the Formula 1 ; (ii) a nonaqueous solvent; and (iii) an alkali metal ion containing substance.
  • the present invention provides a gel polymer electrolyte, which comprises (i) an anion receptor of the Formula 1; (ii) a polymer support; (iii) a nonaqueous solvent; and (iv) an alkali metal ion containing substance.
  • the present invention provides a solid polymer electrolyte, which comprises (i) an anion receptor of the Formula 1 ; (ii) a polymer selected from the group consisting of net-shaped polymers, comb-shaped polymers and branched polymers, or a crosslinkable polymer; and (iii) an alkali metal ion containing substance.
  • the solid polymer electrolyte may further include one or more substance(s) selected from the group consisting of polyalkyleneglycol dialkylether, a nonaqueous solvent and a mixture thereof.
  • the nonaqueous solvent used for the electrolyte includes ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate, ether, organic carbonate, lactone, formate, ester, sulfonate, nitrite, oxazolidinone, tetrahydrofuran, 2- methyltetrahydrofuran, 4-methyl-l,3-dioxolane, 1,3-dioxolane, 1,2-dimethoxylethane,
  • the alkali metal ion containing substance includes LiSO 3 CF 3 , LiCOOC 2 Fs, LiN(SO 2 CF 3 ) 2 , LiC(SO 2 CF 3 ) 3 , LiClO 4 , LiAsF 6 , LiBF 4 , LiPF 6 , LiSbF 6 , LiI, LiBr, LiCl or a mixture thereof.
  • PAN polyacrylonitrile
  • PVDF polyvinylidenfluoride
  • the net-shaped, comb-shaped or branched polymer compounds used in the solid polymer electrolyte but flexible inorganic polymers or linear polyethers are preferred examples.
  • the crosslinkable polymer compound a compound having main chain of a flexible inorganic polymer or a linear polyether as a backbone, and a terminal group selected from the group consisting of acryl, epoxy, trimethylsilyl, silanol, vinylmethyl and divinylmonomethyl is used.
  • the flexible inorganic polymer is preferably polysiloxane or polyphosphagen, and the linear polyether is preferably a polyalkylene oxide.
  • crosslinkable polymer compound examples include bisphenol A ethoxylate dimethacrylate represented by the following Formula 3 or TA-IO represented by the following Formula 4 disclosed in Korean Patent Registration No. 10-0419864: [Formula 3]
  • polyalkyleneglycol dialkylether or a nonaqueous solvent contained in the solid polymer electrolyte is used as a plasticizer.
  • the polyalkyleneglycol dialkylether include polyethyleneglycol dimethylether (PEGDME), polyethyleneglycol diethylether, polyethyleneglycol dipropylether, polyethyleneglycol dibutylether, polyethyleneglycol diglycidylether, polypropyleneglycol dimethylether, polypropyleneglycol diglycidylether, polypropyleneglycol/polyethyleneglycol copolymer terminated with dibuthylether, and polyethyleneglycol/polypropyleneglycol/polyethyleneglycol copolymer terminated with dibutylether.
  • PEGDME polyethyleneglycol dimethylether
  • polyethyleneglycol diethylether polyethyleneglycol dipropylether
  • polyethyleneglycol dibutylether polyethyleneglycol diglycidy
  • the solid polymer electrolyte contains a crosslmkable polymer compound, it further comprises a curing initiator.
  • a photocuring initiator As for the curing initiator, a photocuring initiator, a heat-curing initiator, or a mixture thereof can be used.
  • Preferred examples of the photocuring initiator is selected from the group consisting of dimethoxyphenyl acetophenone (DMPA), t-butylperoxypivalate, ethyl benzoin ether, isopropyl benzoin ether, ⁇ -methyl bezoin ethyl ether, benzoin phenyl ether,
  • DMPA dimethoxyphenyl acetophenone
  • t-butylperoxypivalate ethyl benzoin ether
  • isopropyl benzoin ether ⁇ -methyl bezoin ethyl ether
  • benzoin phenyl ether benzoin phenyl ether
  • heat-curing initiator examples include azoisobutyrontrile compounds, peroxide compounds or mixtures thereof.
  • the electrolyte of the present invention preferably contains 0.5 - 86.5 parts by weight of the anion receptor, and 3 - 60 parts by weight of the alkali metal ion containing substance.
  • the gel polymer electrolyte of the present invention preferably contains 5 - 40 parts by weight of the polymer support.
  • the solid polymer electrolyte of the present invention preferably contains 10 - 95 parts by weight of a polymer compound selected from the net-shaped, comb-shaped and branched polymer compounds, or 10-95 parts by weight of a crosslinkable polymer compound, and 0.5 - 5 parts by weight of a curing initiator.
  • the solid polymer electrolyte of the present invention preferably contains 10 - 50 parts by weight of one or more substance(s) selected from the group consisting of polyalkyleneglycol dialkylether, a nonaqueous solvent and a mixture thereof.
  • the present invention provides an electrochemical cell containing the above anion receptor.
  • a cell using the liquid or gel polymer electrolyte of the present invention is composed of an anode, a cathode, and a separator, while a cell using the solid polymer electrolyte is composed of an anode and a cathode.
  • a cathode and an anode used in the electrochemical cell of the present invention are manufactured by any known method of manufacturing cathodes and anodes used in conventional cells. Also, the components of the electrochemical cell of the present invention can be assembled by any known method.
  • the cathode is made of a material selected from the group that consists of lithium;
  • lithium alloys such as Li-Al, Li-Si, or Li-Cd
  • lithium-carbon intercalation compounds lithium-graphite intercalation compounds
  • lithium metal oxide intercalation compounds such as Li x WO 2 or LiMoO 2
  • lithium metal sulfide intercalation compounds such as Li-Al, Li-Si, or Li-Cd
  • LiTiS 2 LiTiS 2 ; mixtures thereof; and mixtures of these and alkali metals.
  • the anode is made of a material selected from the group that consists of transition metal oxides, transition metal chalcogenides, poly(carbondisulfide)polymers, organic disulfide redox polymers, polyaniline, organic disulfide/polyaniline complexes, and mixtures of these and oxychlorides.
  • a primary cell composed of a nonaqueous liquid electrolyte containing the anion receptor of the present invention is composed of: (i) a cathode made of a material selected from the group consisting of lithium, lithium alloys, lithium-carbon intercalation compounds, lithium-graphite intercalation compounds, lithium metal oxide intercalation compounds, mixtures thereof, and alkali metals;
  • an anode made of a material selected from the group consisting of transition metal oxides, transition metal chalcogenides, poly(carbondisulf ⁇ de)polymers, organic disulfide redox polymers, polyaniline, organic disulfide/polyaniline complexes, and oxychlorides, such as, SO 2 , CuO, CuS, Ag 2 CrO 4 , 1 2 , PbI 2 , PbS, SOCl 2 , V 2 O 5 , MoO 3 , MnO 2 and polycarbon monofluoride (CF) n ;
  • a secondary cell composed of a nonaqueous liquid electrolyte
  • containing the anion receptor of the present invention is composed of:
  • a cathode containing lithium metals or materials capable of reversibly reacting with lithium metal including: lithium; lithium alloys, such as Li-Al, Li-Si, or Li-Cd; lithium-carbon intercalation compounds; lithium-graphite intercalation compounds; lithium metal oxide intercalation compounds, such as Li x WO 2 or LiMoO 2 ; and lithium metal
  • sulfide intercalation compounds such as LiTiS 2 ;
  • an anode containing transition metal oxides capable of intercalating lithium such as, Li 2 5 V 6 Oi 3 , Li 1-2 V 2 Os, LiCoO 2 , LiNiO 2 , LiNi i -x M x O 2 (wherein M is Co, Mg, Al or Ti), LiMn 2 O 4 or LiMnO 2 and the like; transition metal halides; or chalcogenides, such as, LiNbSe 3 , LiTiS 2 , LiMoS 2 and the like; (iii) a nonaqueous liquid electrolyte described above; and
  • the secondary cell composed of a gel polymer electrolyte containing the anion receptor of the present invention comprises a gel polymer electrolyte of the present invention in addition to a cathode, an anode, and a separator used in a secondary cell composed of the above nonaqueous liquid electrolyte.
  • the secondary cell composed of a solid polymer electrolyte containing the anion receptor of the present invention comprises a solid polymer electrolyte of the present invention in addition to a cathode, an anode, and a separator used in a secondary cell
  • the present invention provides a polymer electrolyte film (membrane) using an electrolyte of the present invention.
  • a preparation method of a gel or solid polymer electrolyte film (membrane) containing the components of the present invention is as follows:
  • a nonaqueous solvent, an anion receptor of the Formula 1 and an alkali metal ion containing substance are mixed in a vessel at an appropriate mixing ratio, and are stirred by a stirrer.
  • a polymer support is then added to the solution and mixed together. If necessary, heat can be applied to completely dissolve the polymer support in the solution.
  • a composite mixture for preparing a gel polymer electrolyte film is made.
  • the solution thusly prepared is coated onto a support substrate made of glass or polyethylene, or a commercially available Mylar film to an appropriate thickness. The coated substrate is dried, exposed to electron rays, UV rays or
  • an anion receptor or polyalkyleneglycol dialkylether or a nonaqueous solvent and an alkali metal ion containing material are mixed in a vessel at an appropriate mixing ratio, and are stirred by a stirrer. Then, a net-shaped, branched or comb-shaped polymer compound or a crosslinkable polymer compound is added to the solution and is mixed together. If necessary, heat can be applied to completely dissolve the net-shaped, branched or comb-shaped polymer compound in the solution.
  • a curing initiator can be added to the solution when the crosslinkable polymer is used, hi this manner, a composite mixture for preparing a solid polymer electrolyte film is made.
  • the solution thusly prepared is coated onto a support substrate made of glass or polyethylene, or a commercially available Mylar film to an appropriate thickness.
  • the coated substrate is dried, exposed to electron rays, UV rays
  • Another example of the preparation method for a film is as follows. After the support substrate is coated with the composite mixture, a spacer for regulating the thickness is fixed on both ends of the support substrate. Then, another support substrate is placed thereon and is hardened with the radiator or a heat source to prepare a gel or solid polymer electrolyte film.
  • FIG. 1 is a graph showing a relation between ionic conductivities and temperature changes in solid polymer electrolytes of the present invention and of comparative examples (Experimental example 4);
  • FIG. 2 is a graph showing lithium cycling performance of cells of the present invention and of comparative examples (Experimental example 5).
  • Anion receptors (Example 13 - 47) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1 and 7-12 in the weight ratio shown in Table 1 below. [Table 1]
  • Anion receptors (Example 48 - 88) of the Formula 1 of the present invention were prepared using the procedures described in Examples 3 and 7-12 in the weight ratio shown in Table 2 below. [Table 2] C 4 -2 DCN -
  • Anion receptors (Example 89 - 129) of the Formula 1 of the present invention were prepared using the procedures described in Examples 4 and 7-12 in the weight ratio shown in Table 3 below. [Table 3]
  • Anion receptors (Example 130 - 170) of the Formula 1 of the present invention were prepared using the procedures described in Examples 5 and 7-12 in the weight ratio shown in Table 4 below. [Table 4]
  • Anion receptors (Example 171 - 211) of the Formula 1 of the present invention were prepared using the procedures described in Examples 6 and 7-12 in the weight ratio shown in Table 5 below. [Table 5]
  • Anion receptors (Example 212 - 227) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 3 and 7-12 in the weight ratio shown in Table 6 below. [Table 6]
  • Anion receptors (Example 228 - 243) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 4 and 7-12 in the weight ratio shown in Table 7 below. [Table 7]
  • Anion receptors (Example 244 - 259) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 5 and 7-12 in the weight ratio shown in Table 8 below. [Table 8]
  • Anion receptors (Example 260 - 275) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 6 and 7-12 in the weight ratio shown in Table 9 below. [Table 9]
  • Anion receptors (Example 276 - 291) of the Formula 1 of the present invention were prepared using the procedures described in Examples 3, 4 and 7-12 in the weight ratio shown in Table 10 below. [Table 10]
  • Anion receptors (Example 292 - 307) of the Formula 1 of the present invention were prepared using the procedures described in Examples 3, 5 and 7-12 in the weight ratio shown in Table 11 below. [Table 11]
  • Anion receptors (Example 308 - 323) of the Formula 1 of the present invention were prepared using the procedures described in Examples 3, 6 and 7-12 in the weight ratio shown in Table 12 below. [Table 12]
  • Anion receptors (Example 324 - 339) of the Formula 1 of the present invention were prepared using the procedures described in Examples 4, 5 and 7-12 in the weight ratio shown in Table 13 below. [Table 13]
  • Anion receptors (Example 340 - 355) of the Formula 1 of the present invention were prepared using the procedures described in Examples 4, 6 and 7-12 in the weight ratio shown in Table 14 below. [Table 14]
  • Anion receptors (Example 356 - 371) of the Formula 1 of the present invention were prepared using the procedures described in Examples 5, 6 and 7-12 in the weight ratio shown in Table 15 below. [Table 15]
  • Anion receptors (Example 372 - 377) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 3, 6 and 7-12 in the weight ratio shown in Table 16 below. [Table 16]
  • Anion receptors (Example 378 - 383) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 4, 6 and 7-12 in the weight ratio shown in Table 17 below. [Table 17]
  • Anion receptors (Example 384 - 389) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 5, 6 and 7-12 in the weight ratio shown in Table 18 below. [Table 18]
  • Anion receptors (Example 390 - 395) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 3, 5 and 7-12 in the weight ratio shown in Table 19 below. [Table 19]
  • Anion receptors (Example 396 - 401) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 4, 5 and 7-12 in the weight ratio shown in Table 20 below. [Table 20]
  • Anion receptors (Example 402 - 407) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 3, 4 and 7-12 in the weight ratio shown in Table 21 below. [Table 21]
  • Anion receptors (Example 408 - 412) of the Formula 1 of the present invention were prepared using the procedures described in Examples 1, 3, 4, 5 and 6 in the weight ratio shown in Table 22 below. [Table 22]
  • Example 414 Manufacture of Conductive Thin Film (2) The same procedure of Example 413 was repeated, with the exception that 3.0g of the anion receptor Q-4TFSA obtained from Example 1 was replaced by 1.5g of C 4 -4TFSA and 1.5g of the anion receptor C 4 -4TFSI obtained from Example 2 to prepare a solid polymer electrolyte.
  • Example 415 Manufacture of Conductive Film (3) The same procedure of Example 413 was repeated, with TA- 10 of the Formula 4 instead of the compound of the Formula 3 used as a crosslinking agent to prepare a solid polymer electrolyte.
  • Example 416 Manufacture of Conductive Thin Film (2) The same procedure of Example 413 was repeated, with the exception that 3.0g of the anion receptor Q-4TFSA obtained from Example 1 was replaced by 1.5g of C 4 -4TFSA and 1.5g of the anion receptor C 4 -4TFSI obtained from Example 2 to prepare a solid polymer electrolyte.
  • Example 415 Manufacture of Conductive Film (3) The same procedure
  • Example 413 Manufacture of Conductive Thin Film (4) The same procedure of Example 413 was repeated, with the exception that 3.0g of the anion receptor C 4 -4TFSA obtained from Example 1 was replaced by 1.5g of Q-4TFSA and 1.5g of the anion receptor C 4 -4TFSI obtained from Example 2 to prepare a solid polymer electrolyte. Examples 417 - 431. Manufacture of Conductive Thin Film (5 - 19)
  • Example 413 The same procedure of Example 413 was repeated, with the exception that compositions of compounds used are as shown in the following Table 23 to prepare a solid polymer electrolyte. Comparative Examples 1 - 2. Manufacture of Film without Anion Receptors (1 - 2)
  • Example 413 The same procedure of Example 413 was repeated using the compositions of compounds shown in the following Table 23 to prepare a solid polymer electrolyte. As shown in Table 23, polymer electrolytes of Comparative Examples do not contain anion receptors. [Table 23]
  • Ionic conductivities of the solid polymer electrolyte films obtained from the above examples were measured as follows. First, a solid polymer electrolyte composition was coated onto a conductive glass substrate or onto a lithium-copper foil, photohardened, and dried sufficiently. Under nitrogen atmosphere, AC impedance between band shaped (or sandwich shaped) electrodes was measured, and the measurement was analyzed with a frequency response analyzer to interpret complex impedance. To manufacture the band shaped electrodes, masking tapes having a width between 0.5mm and 2mm were adhered to the center of a conductive glass (ITO) at intervals of 0.5 - 2mm, etched in an etching solution, washed and dried.
  • ITO conductive glass
  • Ionic conductivity of the solid polymer electrolyte film thusly obtained was measured at a temperature of 3O 0 C. Results are shown in Table 24. According to Table 24, ionic conductivity of the film of Example 418 is greater than that of the film of Example 417. Similarly, ionic conductivity of Example 420 is greater than that of Example 419. These results prove that ionic conductivity improves proportionally to the concentration of anion receptors. [Table 24]
  • Ionic conductivity measurement results of polymer films of the Examples 422 and 423 at a temperature of 3O 0 C are shown in the following Table 25.
  • the test was carried out using the same procedure described in Experimental Example 1 to find out conditions for maximizing ion conductivities of polymer films, hi particularly, plasticizers and anion receptors were used together to make polymer films. It turned out that Example 2 which used both anion receptors and plasticizers exhibited superior ionic conductivity to that of Example 1 which used anion receptors only. [Table 25]
  • Example 413 The same procedure in Example 413 was repeated to manufacture solid polymer electrolyte films using anion receptors obtained from Examples 3 - 7, 11, 12 and 28. Using the same procedure described in Experimental Example 1, ionic conductivities of the films were measured. The measurement results are shown in the following Table 26. As shown in Table 26, the results proved that solid polymer electrolytes containing various anion receptors exhibited superior ionic conductivities. [Table 26]
  • Ionic conductivities of films obtained from Comparative Examples 1 and 2 without anion receptors were measured using the same procedure described in Experimental Example 1. Ionic conductivity measurement results of the solid polymer electrolyte films at a temperature of 3O 0 C are shown in Table 27. Comparing the measurement results shown in Table 27 with the measurement results shown in Tables 24 - 26, one can find out that ionic conductivities of films without anion receptors are very low. [Table 27]
  • Example 431 Manufacture of Cell Using Liquid Electrolyte with Anion Receptors
  • 0.015g of the anion receptor C 4 -4TFSI obtained from Example 2 was mixed with 1.Og of an organic solvent EC/DMC/EMC (1:1:1, IM LiPF 6 ).
  • a polypropylene separator impregnated with the above solution was inserted between a LiCoO 2 anode and a graphite carbon cathode in a dry room (humidity below 3%) and vacuum-sealed to assemble a cell.
  • the LiCoO 2 anode was prepared by coating an aluminum foil with a mixture of 94wt% LiCoO 2 (manufactured by Nippon Chemical Industry), 3wt% of acetylene black, and 3wt% of polyvinylidenfluoride (PVDF).
  • Comparative Example 3 Manufacture of Cell Using Liquid Electrolyte without Anion Receptors The same procedure described in Example 431 was repeated, with the exception that the separator impregnated with an organic solvent EC/DMC/DEC (1:1 :1, IM LiPF 6 ) only was inserted between a LiCoO 2 anode and a graphite carbon cathode. Experimental Example 5. Cell Lithium Cycling Performance and Efficiency Test Lithium cycling performance and efficiency of cells manufactured in Example 431 of the present invention and Comparative Example 3 were tested at room temperature using Maccor 4000. Charging and discharging were carried out to 0.2, 0.5 and 1C, respectively. The cells were charged and discharged anywhere between 3.0V and 4.2V at a predetermined current density of 0.6mA/cm (charging) and 1.5mA/cm (discharging) with respect to a LiCoO 2 counter electrode.
  • FIG. 2 graphically shows a comparison between discharge capacities with respect to the number of cyclings of cells manufactured using electrolytes inclusive of the anion receptor C 4 -4TFSI (Example 2) and those of cells manufactured using electrolytes exclusive of the anion receptor. As shown in FIG. 2, it turned out that the cells manufactured using electrolytes of the anion receptor C 4 -4TFSI exhibited higher capacity and superior stability.
  • the novel anion receptor of the present invention can be used as an additive to enhance lithium cycling performance and efficiency of liquid electrolytes for high capacity lithium-ion batteries and cells.
  • the polymer electrolytes containing the novel anion receptor offer substantially enhanced ionic conductivities and electrochemical stabilities at room temperature, so they are for a broad range of applications which include small lithium polymer secondary cells used in portable information terminals, e.g., cell phones, notebook computers, etc., and all

Abstract

Cette invention concerne un récepteur anionique et des électrolytes le renfermant. Ce récepteur anionique d'un type nouveau est un composé siloxane cyclique dont une amine est substituée par des groupes accepteurs délectons ou au moins l'un d'un groupe d'oxyde de polyalkylène, d'un groupe cyano ou d'un groupe carbonate de propylène en tant que branche latérale en plus de l'amine substituée par les groupes accepteurs d'électrons. L'adjonction du récepteur anionique à l'électrolyte a pour effet d'accroître la conductivité ionique et le nombre de transfert de cations, ce qui augmente la stabilité électrochimique des batteries à métal alcalin utilisant les électrolytes.
PCT/KR2006/002161 2005-06-03 2006-06-05 Recepteur anionique et electrolyte utilisant ce recepteur WO2006129991A1 (fr)

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WO2007091817A1 (fr) * 2006-02-06 2007-08-16 Hee Jung Kim Récepteur d'anions et électrolyte faisant appel à ce récepteur
KR101451805B1 (ko) 2008-01-25 2014-10-16 삼성에스디아이 주식회사 리튬이차전지 전해질용 첨가제, 이를 포함하는 유기 전해액및 상기 전해액을 채용한 리튬 전지

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US10559827B2 (en) 2013-12-03 2020-02-11 Ionic Materials, Inc. Electrochemical cell having solid ionically conducting polymer material
US9819053B1 (en) 2012-04-11 2017-11-14 Ionic Materials, Inc. Solid electrolyte high energy battery
US11152657B2 (en) 2012-04-11 2021-10-19 Ionic Materials, Inc. Alkaline metal-air battery cathode
US11319411B2 (en) 2012-04-11 2022-05-03 Ionic Materials, Inc. Solid ionically conducting polymer material
US11251455B2 (en) 2012-04-11 2022-02-15 Ionic Materials, Inc. Solid ionically conducting polymer material
EP3078069B9 (fr) * 2013-12-03 2021-05-19 Ionic Materials, Inc. Matériau polymère solide à conduction ionique, et applications
JP7109879B2 (ja) * 2014-04-01 2022-08-01 イオニツク・マテリアルズ・インコーポレーテツド 高容量高分子の陰極および該陰極を含む高エネルギー密度の再充電可能な電池
JP6944379B2 (ja) 2015-06-04 2021-10-06 イオニツク・マテリアルズ・インコーポレーテツド 固体状バイポーラ電池
EP3304636A4 (fr) 2015-06-04 2018-11-07 Ionic Materials, Inc. Batterie au lithium métal à électrolyte solide polymère
US11342559B2 (en) 2015-06-08 2022-05-24 Ionic Materials, Inc. Battery with polyvalent metal anode
JP6991861B2 (ja) 2015-06-08 2022-02-03 イオニツク・マテリアルズ・インコーポレーテツド アルミニウム負極および固体ポリマー電解質を有するバッテリー
WO2018140552A1 (fr) 2017-01-26 2018-08-02 Ionic Materials, Inc. Cathode de batterie alcaline avec électrolyte polymère solide

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WO2007091817A1 (fr) * 2006-02-06 2007-08-16 Hee Jung Kim Récepteur d'anions et électrolyte faisant appel à ce récepteur
KR101451805B1 (ko) 2008-01-25 2014-10-16 삼성에스디아이 주식회사 리튬이차전지 전해질용 첨가제, 이를 포함하는 유기 전해액및 상기 전해액을 채용한 리튬 전지

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